ZA200109114B - Solvates of pymetrozine. - Google Patents
Solvates of pymetrozine. Download PDFInfo
- Publication number
- ZA200109114B ZA200109114B ZA200109114A ZA200109114A ZA200109114B ZA 200109114 B ZA200109114 B ZA 200109114B ZA 200109114 A ZA200109114 A ZA 200109114A ZA 200109114 A ZA200109114 A ZA 200109114A ZA 200109114 B ZA200109114 B ZA 200109114B
- Authority
- ZA
- South Africa
- Prior art keywords
- weak
- formula
- pymetrozine
- water
- compound
- Prior art date
Links
- 239000005925 Pymetrozine Substances 0.000 title description 57
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 title description 50
- 239000012453 solvate Substances 0.000 title description 17
- 239000000203 mixture Substances 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 22
- 150000003839 salts Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000004480 active ingredient Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 230000000361 pesticidal effect Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000007614 solvation Methods 0.000 claims description 8
- 241000607479 Yersinia pestis Species 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229960004132 diethyl ether Drugs 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZRECPFOSZXDFDT-UHFFFAOYSA-N 1-decylpyrrolidin-2-one Chemical compound CCCCCCCCCCN1CCCC1=O ZRECPFOSZXDFDT-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 238000009472 formulation Methods 0.000 description 37
- 239000008187 granular material Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- -1 mineral acids Chemical class 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 7
- 239000000546 pharmaceutical excipient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 6
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
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- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
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- 229920005610 lignin Polymers 0.000 description 4
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- 238000003860 storage Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- HCWYXKWQOMTBKY-UHFFFAOYSA-N calcium;dodecyl benzenesulfonate Chemical compound [Ca].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 HCWYXKWQOMTBKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PQZTVWVYCLIIJY-UHFFFAOYSA-N diethyl(propyl)amine Chemical group CCCN(CC)CC PQZTVWVYCLIIJY-UHFFFAOYSA-N 0.000 description 1
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Description
« =
Solvates of Pymetrozine
The present invention relates to novel, insecticidally active solvates of pymetrozine, a method of producing them, compositions containing these compounds, a method of producing these compositions, a method of controlling pests with the said compositions, and their use in the control of animal pests, especially insects and members of the order Acarina, particularly in crops of cultivated plants.
Various solvates, for example hydrates, of a chemical compound can exhibit very different physical properties, which may lead to unforeseeable problems during technical preparation and processing of these compounds. The characteristics of such solvates frequently have a crucial influence on the separating ability (filtration), stirrability (crystal volume), surface activity (foaming), rate of drying, solubility, quality, formulating ability and storage stability (e.g. hygroscopy) of for example pesticidally active compounds. For example, the grinding and formulating properties, as well as the handling ability of such pesticidal mixtures, may be completely different depending on the respective solvatising. Since, in the various stages of synthesis of a preparation process, different physical properties of the respective synthesis products are of importance, it is especially advantageous to find the optimally suited solvation form for the respective stage of synthesis.
Pymetrozine is known for example from US-P-4931439, in which the preparation is des- cribed in example P3. However, it cannot be assumed from this example that the product ) obtained had been solvated with ethanol, diethylether or water, even though the product had come into contact with ethanol, diethylether and water in the course of its preparation. At the end of the preparation process, the compound was dried, and it was used in the formulation examples as an essentially water-free and solvent-free product. Physical parameters such as temperature, humidity and pressure, which are crucial for the specific preparation of certain solvates, are not indicated anywhere in the said patent specification.
It is therefore the aim of the present invention to prepare solvates, in particular hydrates, and salts of such solvates of pymetrozine, the characteristics of which show the advantages mentioned initially, especially in the production and handling of pesticidal mixtures, parti- cularly granutates.
Accordingly, the present invention relates to compounds of formula
- _N opr]
A PY ® Le (Ho),
N Oo ; wherein r and s, independently of each other, signify any value between 0.00 and 12.00: and
L is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, cyclohexanol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl . sulphoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2- ) pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methylpropyl ketone, acetophenone, cyclohexanone, methylene chloride, trichloromethane, trichloro- : ethane, tetrahydrofuran, diethylether, 1,2-dimethoxyethane, dioxane, methyl-tert.-butylether, ethanolamine, pyridine, chlorobenzene, toluene, xylene or tetramethylurea; with the proviso that r and s are not simultaneously 0; in each case in free form or in salt form, and their tautomers, in each case in free form or in salt form, a method for the preparation and usage of these compounds, their salts and their tautomers; pesticides whose active ingredient is selected from these compounds and their tautomers; and a method for the preparation of these solvates and where appropriate their salts, a method for the preparation of these compositions and their usage. . in the following, a distinction will be made between the compound of formula (1) or the salts thereof, in which r and s are not simultaneously 0, and pymetrozine, which is the solvate-free compound (in which r and s are simultaneously 0).
Compounds of formula (I) have several basic centres. They may therefore form acid addition salts. These are formed for example with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulphuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as C,-C,-alkanecarboxylic acids optionally substituted for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or
. 4 ® with organic sulphonic acids, such as C,-C.alkanesulphonic or arylsulphonic acids optionally substituted for example by halogen, e.g. methanesulphonic or p-toluenesulphonic acid. In addition, compounds of formula (I) may form salts with bases. Suitable salts with bases are for example metal salts, such as alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
In this case, on the one hand salts with formic acid, acetic acid and lactic acid are preferred, and on the other hand the sodium, potassium, magnesium and calcium salts are preferred, ) especially sodium salts. On the other hand, the compound of formuta (I) in free form, i.e. in which ris 0, is also preferred.
Compounds (I) have also one acid group and can therefore form salts with bases. Suitable salts with bases are, for example, metal salts including metal complexes, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, but also comples salts with for instance copper, nickel of iron; or saits with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower } alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. If appropriate, corresponding inner salts can furthermore be formed. Agrochemically advantageous salts ’ are preferred in the context of the invention. Hereinabove and hereinbelow, the compounds (I) in free form are to be understood as including the corresponding salts, and the salts are to be understood as including the free compounds (1). In each case the free form is in general preferred. .
Further preferred compounds of formula (I) are characterised in that L signifies methanol; especially wherein L is methanol and s is 0.
Additionally preferred compounds of formula (I) are characterised in that r signifies 0 and s is 0.5,0.75,1, 1.25, 1.5, 1.75, 2,2.25, 2.5, 2.75, 3, 3.25, 3.5,3.75,4,5,6, 7,8 or 12; especially 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 5,6, 7, 8 or 12; in particular 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 5 or 6; most preferably 1.5, 2, 2.5, 3, 3.5 or 4;
most particularly 2.
One especially preferred object of the invention is a compound of formula (1), in which ris 0 and s is 2 (pymetrozine dihydrate), and which shows the reflections listed in table 1 in the
X-ray powder pattern.
Table 1: X-ray powder data of pymetrozine dihydrate : d (A) intensity 12.4 average 71 weak 6.8 very strong 6.3 weak 6.2 average 5.82 very weak 5.40 average 5.14 very weak 4.85 weak 4.68 very weak 4.52 very weak 4.31 very weak ’ 4.14 weak 4.08 very weak . 3.96 very weak 3.83 very weak 3.71 very weak 3.58 weak 3.47 very strong 3.44 very strong 3.25 strong 3.21 weak 3.09 average 3.03 weak 2.99 weak
. vow d (A) Intensity 2.90 weak 2.82 weak 2.76 weak 2.57 weak
A further preferred object of the invention is a compound of formula (I) in which ris 1 and s is 0 and L is methanol (pymetrozine methanolate), and which shows the following reflections in the X-ray powder pattern:
Table 2: X-ray powder data of pymetrozine methanolate d (A) Intensity 8.4 strong ) 6.3 very weak 5.96 weak 5.51 very weak 5.31 very weak 5.18 very weak 4.97 very weak : 4.81 very weak 4.55 average . 4.42 weak 4.22 weak 3.94 very weak 3.75 very weak 3.48 strong 3.38 very strong 3.25 weak 3.08 weak 3.04 weak 2.98 very weak 2.94 very weak 2.84 very weak 2.81 very weak iL ¢ a d (A) Intensity 2.77 very weak 2.74 very weak 2.71 very weak 2.66 weak
A further object of the invention relates to a new modification of pymetrozine (hereinafter referred to as the pymetrozine 3-modification), in which r and s are 0. This new modification is obtained whereby a sample of pymetrozine, which has been isolated during preparation from an aqueous-methanolic suspension, is dried at 120°C to 150°C
Table 3: X-ray powder data of pymetrozine -modification d(A) Intensity 9.7 average ’ 8.4 very weak 5.87 strong 5.57 average 5.14 very weak 4.96 weak 4.86 average . 4.69 very weak 4.40 average } 4.28 very weak 4.23 very weak 3.83 weak 3.73 weak 3.66 weak 3.49 strong 3.34 very strong 3.28 shoulder 3.06 weak 2.95 very weak 2.82 average 2.65 weak
» toa 2.60 very weak 2.53 very weak 2.48 very weak 2.30 weak 2.25 very weak 2.20 very weak 2.11 weak 2.07 weak 2.00 weak
The X-ray powder data of the known a-modification of pymetrozine are also given below for comparison: } Table 4: X-ray powder data of pymetrozine a-modification d(A) Intensity 11.9 weak a7 average 7.6 average 6.4 very weak 6.1 average 5.95 average 5.65 average : 5.26 average 4.76 weak 4.49 weak 4.43 very weak - 4.37 weak 4.11 strong 3.99 very strong 3.81 weak 3.57 weak 3.52 weak 3.48 strong 3.34 very strong wor, d(A) Intensity 3.26 very weak : 3.14 strong oo 3.07 very weak 2.99 average 2.90 weak 2.82 average 2.80 weak 2.75 weak 2.66 very weak 2.61 : weak
Measurement of the X-ray powder patterns was made with an X'Pert powder diffractometer (Philips) with TTK camera (Anton Paar), using Cu radiation (A = 1.54060A). Measurements . of the dihydrate of table 1 and of the anhydrates of tables 3 and 4 were made at room " temperature. The measurement of the methanolate of table 2 was made whilst cooling (5° - 8°C) on a sample sealed with Kapton film.
It has now surprisingly been shown that dried, water-free and solvent-free pymetrozine is in a position to reversibly take up water or a solvent from the atmosphere or during mixing or grinding. It was found that, at room temperature and at a relative humidity of less than ’ ca. 10%, water-containing pymetrozine gives up the water completely, and at a relative humidity of between 60% and 70%, takes up ca. 16 to 17% by weight of water again. The above-mentioned water content of 16 to 17% by weight corresponds very well to a dihydrate.
Even pesticidal formulations that contain water-free and solvent-free pymetrozine take up usually water or the corresponding solvent from the atmosphere when left to stand under sufficiently high vapour pressure. This solvation, in particular water absorption, of formu- lations, in particular of water-dispersible powders and granulates, especially granulates, can lead to problems when handling and storing the pesticidal compositions, but these problems do not arise if pymetrozine in the form of a defined solvate or in the form of the above- mentioned 3-modification is either introduced into the production process of the pesticidal composition, or is produced in an appropriate way during the afore-mentioned production process. For example, such formuiations no longer have to be kept in airtight containers, and once containers have been opened, they do not have to be tightly sealed again in order to retain the quality of the goods.
a.
In addition, the production of the formulations according to the invention with a relatively high water content or when using the B-modification of pymetrozine is simpler than the production of essentially water-free formulations or when using the a-modification, since production is generally effected in such a way that water is added in the formulation step and subsequent- ly has to be removed again. To completely or almost completely remove the water involves considerable disadvantages, such as the high energy consumption, prolonged production times, greater use of equipment, etc.
A ready formulation of pymetrozine with a water content of ca. 10 % by weight under normal conditions has only a very insignificant tendency to absorb moisture from the air, whereas a . formutation whose water proportion has been reduced during production to less than 5 % or which has been manufactured starting by using essentially waterfree ingredients is very hy- } groscopic. Long-term storage of formulations having a water content of less than ca. 5 % by weight requires packaging that is completely sealed against water vapour and has to be pro- duced using correspondingly greater effort. When it is disposed of, it presents greater prob- lems than the conventional containers that are not absolutely watertight.
In addition, packages whose contents cannot be used up at once are generally not resealed in a sufficiently watertight manner. It is therefore unavoidable for water to be absorbed by the . water-free formulation.
When a water-free formulation absorbs water, its quality is significantly reduced within a period of weeks to months. This means that the official figures relating to the proportion of active ingredient in the formulation can no longer be observed under some circumstances.
Therefore, the absorption of water by the water-free formulation can lead to unsaleable goods when stored by the manufacturer or retailer, without the active ingredient actually decomposing.
Spontaneity: The quality of a water-dispersible granulate is determined to a substantial ex- tent by its user friendliness. Accordingly, the user expects the granulate to completely break down into its primary particles within a few minutes of mixing up the spray liquor. When for- mulating pymetrozine, this characteristic known as spontaneity is not obtained if a formu- lation is used which is originally water-free or of low water content, but has absorbed water again during storage. In contrast to the essentially water-free formulations, after storing for a period of 7 days in the appropriate test apparatus, the formulations according to the inven-
FO tion show a complete breakdown of the granulates into the primary particles within a few minutes.
Table 5: Comparison of spontaneity after various periods (test carried out analogously to
CIPAC MT 174); pymetrozine granulates with a content of active ingredient of 50 % by ; weight
ES alert : weight storage in % days at room temperature in %
SR I = KE i weight
Commer | si | es | w | wz | wm | a + [oman | 0s |e | we | war | ew | ww _ When measuring the spontaneity, first the spray liquor is produced by shaking the compo- ition in a cylinder in the presence of a specified amount of water. After 0.5 or 1 minutes, 90% - of the liquor is suctioned off and the remainder concentrated by evaporation. The residue = obtained is assessed after drying and the amount of the originally used material which is } suspended in the liquor is calculated in %.
Without taking into account the water content, the granulates have the composition as indi- cated in the following example F10 and are produced as indicated therein.
Further advantages of the formulations being claimed according to the invention are improed suspension ability in the spray liquor and improved dispersibility.
A desired solvate may be produced before the active substance is combined with the formu- lation excipients, or alternatively during the formulation procedure by suitably bringing it into contact with the desired amount of a certain solvent or with water. It is therefore possible to use various processes for the specific production of such solvates and of pesticidal compo- sitions containing such solvates. Water-free and solvent-free pymetrozine can for example be agitated or ground in a mixer in an atmosphere having a defined content of water or sol- vent until the desired form is obtained. Or, pymetrozine with a high content of water or sol- vent, which results from a production process, or which has been produced by mixing essen- tially solvent-free and water-free pymetrozine specifically with a larger amount of solvent or water, is dried in a drier to the desired content of solvation agent. These methods of produ- cing solvates, especially hydrates, or pymetrozine, therefore form a further object of the pre- sent invention.
Wort a
Suitable formulations for the compounds of formula (1) are described for example in US-P- 4931439. They are all characterised in that they do not contain any pymetrozine in solvated form.
The formulations, i.e. agents, preparations or compositions which contain an active ingre- dient of formula (1) and one or more solid and/or liquid formulation excipients, likewise form an object of the invention. They are produced for example in a manner known per se, by intimately mixing and/or grinding the active ingredient of formula (i) with the formulation excipients, such as solvents or solid carriers. An alternative, new preparation method, which similarly forms an object of the invention, consists in adding the solvation agent during the . formulation procedure, thus forming the solvate during the formulation process. In an impor- tant variant of this method, the solvation agent can be added in excess, and removed again at the end for example by evaporation, to give the desired value. In the case of certain mixtures, this procedure can significantly simplify the production process. Corresponding compositions produced by this method similarly form an object of the invention.
Surface-active compounds (surfactants) may additionally be used for preparing the formu- jations. Examples of solvents and solid carriers are given e.g. in US-P-4931438. Depending on the type of active ingredient of formula (I) to be formulated, suitable surface-active com- pounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed for example in US-P-4931439.
The insecticidal and acaricidal formulations according to the invention will as a rule contain from 0.1 to 99 % by weight, especially from 1 to 95% by weight, of compound of formula (1), from 1 to 99.9% by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formu- lation excipient, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a h surfactant. Equally preferred are the insecticidal and acaricidal formulations which contain from 0.1 to 94% by weight, especially from 0.1 to 90% by weight, of pymetrozine, from 5 to 30% by weight of solvation agent, from 1 to 94.9% by weight, especially from 5 to 90% by weight, of a solid or liquid formulation excipient, and from 0 to 30% by weight, especially from 0.1 to 25% by weight, of a surfactant.
The pesticidal formulations, especially granulates, that are preferred in particular, are those which contain from 3 to 5% by weight, or those which contain from 30 to 50% by weight of
Cory pymetrozine. Equally preferred are water-dispersible powders, which contain from 25 to 50% by weight of pymetrozine. oe Also preferred are pesticidal formulations, in particular granulates, which contain from 8to 40% by weight, preferably from 8 to 20% by weight, especially from 8 to 14% by weight, of - water. Equally preferred are pesticidal formulations, in particular granulates, which contain from 40 to 60% by weight of pymetrozine, especially 50% by weight of pymetrozine.
Also preferred are wettable powders which contain from 6 to 20% by weight, especially from 8 to 12% by weight, of water, and from 20 to 30% by weight of pymetrozine, especially 25% by weight of pymetrozine.
When specifying the amount of water content, the fact that the formulation excipients them- ) selves often have a certain residual content of water must be taken into consideration. For } this reason, the water content of the formulations actually ascertained is generally a little : . higher than that calculated from the composition of the hydrates. In general the measured : contents are 1 to 5% by weight higher than those calculated. Hereinbefore and hereinafter, a . formulation of pymetrozine that is essentially free of water or of low water content is under- > stood to be a pesticidal mixture containing at most 6% by weight of water, based on the total mixture.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. The compositions may also contain further ingredients, such as stabilisers, e.g. where appropriate epoxidised vegetable oils (epoxidised coconut oil. : rapeseed oil, or soybean oil), activators, antifoams, typically silicone oil, preservatives, viscosity regulators, binders, tackifiers, as well as fertilisers or other active ingredients.
The compounds of formula (1) are usually applied to the plants or the locus thereof in con- centrations of 0.001 to 1.0 kg/ha, preferably 0.1 to 0.6 kg/ha. The concentration required to achieve the desired action can be determined by experimentation. It will depend on the type of action, the development stage of the cultivated plant and of the pest, as well as on the application (locus, time, method), and as a result of these variables can vary over a wide range. As with the type of compositions, the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.
x Un 13 -13-
The compositions which contain the compounds of formula (I) have excellent insecticidal properties, making them suitable for application in crops of cultivated plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantations, rape, maize and rice. Crops will also be understood to mean those crops that have been made tolerant to pesticides by conventional breeding or genetic engineering methods. Pests, especially insects and mem- bers of the order Acarina, that may be controlled with the formulations according to the invention, are described for example in US-P-931439 and in US-P-46145,
The invention is illustrated by the following non-limitative Examples.
Formulation examples % refer to percentages by weight . Example F1: Emulsion concentrates a) b) c) pymetrozine methanolate 25% 4.0% 05% calcium dodecylbenzene sulphonate 5% 8 % 6% castor oil polyethylene glycol ether (36 mol EO) 5% - - tributy! phenol polyethylene glycol ether (30 mol EO) - 4% 4% lactic acid 80 % 71% - formic acid - - 64.5%
N-octylpyrrolidone 7.5% 5% 20 % . Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
Example F2: Solutions a) b) c) i pymetrozine trihydrate 30% 20 % 10 % formic acid 70% - - acetic acid - 80 % - lactic acid - - 90 %
Example F3. Solutions a) b) c) pymetrozine methanolate 30 % 20% 10% formic acid 70 % - - acetic acid - 80 % - tactic acid - - 90 %
The solutions are suitable for use in the form of microdrops. we Example F4: Coated granulates a) b) c) pymetrozine * CH,OH 5% 3% 25% highly dispersed silicic acid 6 % 5% 4% "polyethylene glycol 300 5 % 4% 3% : calcium carbonate 84 % 88 % 90.5 %
The active ingredient is suspended in polyethylene glycol 300, sprayed onto the carrier and ’ - the granulates subsequently powdered off with the silica.
Example F5: Dusts a) b) - pymetrozine dihydrate 2% 5% highly dispersed silicic acid 1% 5% talc 97 % - . kaolin - 90 %
Ready-to-use dusts are obtained by intimately mixing the carriers with the active ingredient and subsequently grinding.
Example F6: Wettable powders a) b) c) pymetrozine dihydrate 25% 50 % 75% sodium lignin sulphonate 5% 8% sodium lauryl sulphate 3% - - sodium diisobutylnaphthalene sulphonate - 6 % 8% octylphenol polyethylene glycol ether (7-8 mol EO) - 2% - highly dispersed silicic acid 5% 10 % 9% kaolin 62 % 27 % -
-15-
The compounds are mixed with the adjuvants and this mixture is ground in a suitable mill to give wettable powders which can be diluted with water to give suspensions of any desired concentration.
Example F7: Wettable granulate a) b) c) pymetrozine dihydrate 30% 40 % 85% sodium lignin sulphonate 30% 30% 12.8% sodium dibutyinaphthalene sulphonate 5% - 20% block polyoxyalkylate 5% 75% - polymeric organic carrier 5% - - antifoam 0.1% 0.2% 02% kaolin 249% - - talc - 22.3% -
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. This mixture is extruded, granulated and then dried in a stream of air.
Example F8: Suspension concentrate pymetrozine dihydrate 40 % propylene glycol 5% : nonylphenol polyethylene glycol ether (15 mol EO) 6 % tristyrylphenol polyglycol ether phosphate triethanolamine 7% . heteropolysaccharide 1% 1,2-benzisothiazoi-3-one 02% silicone oil in the form of a 75% aqueous emulsion 0.8 % water 40 %
The finely ground active ingredient is intimately mixed with the adjuvants. In this way, a suspension concentrate is obtained from which suspensions of any desired concentration can be prepared by dilution with water.
Coy,
Example F9: Preparation of a water-dispersible granulate of the compound of formula (I):
The following substances are admixed and subsequently ground using a conventional mill: 60 % anhydrous pymetrozine 5% sodium dibutyinaphthalene sulphonate % sodium lignin sulphonate 5% sodium sulphate 15% polymeric organic carrier 0.1% perfluoroalkyl phosphoric acid 49% silicon dioxide
The mixture is subsequently mixed with 35-45% by weight water and granulated. After drying to residual moisture of 8 - 12% on a commercial continuous drier, the granulate obtained is . sieved to a defined grain size. Granulates are obtained, which contain the compound of formula (1) in hydrated form. .
Example F10: Preparation of a water-dispersible granulate of the compound of formula (i):
The following substances are admixed. 50 % anhydrous pymetrozine 5% sodium dibutylnaphthalene sulphonate 10 % sodium lignin sulphonate 5% sodium sulphate , 15% polymeric organic carrier 0,1 % perfluoroalkyl phesphoric acid remaining % silicon dioxide
The mixture is subsequently mixed with 50 to 70% by weight water and granulated. After drying to residual moisture of 8 - 12% on a commercial! continuous drier, the granulate obtained is sieved to a defined grain size. Granulates are obtained, which contain the compound of formula (1) in hydrated form.
Preparation examples of solvates of formula (1) and of formulations containing such solvates:
Example P1: Preparation of the compound of formula (1), in which ris 0 and s is 2 (dihydrate of pymetrozine):
TEE
Pymetrozine is stored in a closed container having controlled atmosphere of 89% relative humidity for a period of 10 days. The product is then removed from the container and equilibrated in a laboratory atmosphere. On a thermo-scale, the product obtained shows a weight loss of 13.9% between room temperature and 125°C, which corresponds to two water molecules (theoretical loss 14.2%).
In the X-ray diffractometer using Cu radiation (A 1.54060A) at room temperature, the pattern reproduced in Table 1 is found.
Example P2: Preparation of the compound of formula (1), in which r is 0 and s is 2 (dihydrate of pymetrozine):
In a mixer, a defined amount of water (16% based on water-free pymetrozine) is sprayed ’ evenly onto the active ingredient whilst cooling, and the powder is subsequently slowly stirred until cooled to room temperature.
Example P3: Preparation of the compound of formula (1), in which ris 0 and s is 2 (dihydrate of pymetrozine):
In a rapid-action mixer, a defined amount of water is sprayed evenly onto a mixture of active ingredient and formulation excipients, and after interim storing, the powder is further processed to the final formulation. . Example P4: Preparation of the compound of formula (I), in which ris 0 and s is 2 (dihydrate of pymetrozine): ) In a vessel with stirrer, pymetrozine is suspended in water in the presence of the remaining formulation components, and the mixture is subsequently finely sprayed in a stream of air and dried to residual moisture of 6 - 15%.
Example P5: 0.5 g of pymetrozine are stirred for 9 days at 25°C in 2.5 g of water; then the = suspension is filtered. The dihydrate, which in thermogravimetry shows a weight loss of 12% by weight, is obtained.
Example P6: Preparation of the compound of formula (I), in which ris 1, sis O and L is methanol (methanolate of pymetrozine): 0.488 g of water-free pymetrozine are added at 0°C to 1.909 g of water-free methanol and stirred for 7 days at 0°C. The suspension is filtered through a frit without applying a vacuum.
A sample of the filter cake is immediately measured in the X-ray diffractometer. The pattern t Fl 3 given in Table 2 is obtained.
A thermogravimetric examination between 0°C and 100°C shows a weight loss of 12.4%, which corresponds to one molecule of methanol (theory: 12.8% by weight).
Claims (7)
1. Compounds of formula N PY ® Lo [HO] (0. NG N Oo H wherein r and s, independently of each other, signify any value between 0.00 and 12.00; and L is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, cyclohexanol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl suphoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyi-2- pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methylpropyl ketone, acetophenone, cyclohexanone, methylene chloride, trichloromethane, trichloro- ethane, tetrahydrofuran, diethylether, 1,2-dimethoxyethane, dioxane, methyl-tert.-butylether, ethanolamine, pyridine, chlorobenzene, toluene, xylene or tetramethylurea; : with the proviso that r and s are not simultaneously 0, each in free form or in salt form, and the tautomers thereof, each in free form or in salt form.
2. Compounds of formula (1) according to claim 1, in which L signifies methanol.
3. Compounds of formula (I) according to claim 1, in which ris 0 and s is 2.
4. A pesticidal composition which contains a compound according to anyone of claims 1to 3 of formula (I) and one or more adjuvants.
5. A method of controlling pests, which comprises applying an active ingredient of formula (I) as described in claim 1 or a composition containing this active ingredient in a pesticidally active quantity as described in claim 4 to the pests or to their locus.
1] NY 4
6. Method for the preparation of pesticidal compositions as described in claim 4, which comprises bringing the pesticidal mixture containing the essentially solvate-free compound of formuia (1), wherein r and s are 0, into contact with the solvation agent.
7. Method for the preparation of a compound of formula (1) as described in claim 1, in which the non-solvated, pesticidally active compound is brought into contact with the solvation agent. 8: A pesticidal composition according to claim 4, produced by the method described in claim 6.
7. The use of a composition of claim 4 for the control of pests.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CH90599 | 1999-05-12 |
Publications (1)
Publication Number | Publication Date |
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ZA200109114B true ZA200109114B (en) | 2002-05-08 |
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ID=4197914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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ZA200109114A ZA200109114B (en) | 1999-05-12 | 2001-11-05 | Solvates of pymetrozine. |
Country Status (2)
Country | Link |
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CU (1) | CU23216A3 (en) |
ZA (1) | ZA200109114B (en) |
-
2001
- 2001-11-05 ZA ZA200109114A patent/ZA200109114B/en unknown
- 2001-11-12 CU CU20010254A patent/CU23216A3/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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CU23216A3 (en) | 2007-07-20 |
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